Synthesis, Structures, and Reactivity of Ruthenium Complexes with PNP-pincer Type Phosphaalkene Ligands
Synthesis, Structures, and Reactivity of Ruthenium Complexes with PNP-pincer Type Phosphaalkene Ligands
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DOI：
10.1021/om400126v
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发表时间：
2013-05
期刊：
影响因子：
2.8
通讯作者：
Y. Nakajima;Y. Okamoto;Yung-Hung Chang;F. Ozawa
中科院分区：
文献类型：
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作者：
Y. Nakajima;Y. Okamoto;Yung-Hung Chang;F. Ozawa
2，6-Bis[1-phenyl-2-(2，4，6-tri-tert-butylphenyl)-2-phosphaethenyl]pyridine(BPEP-Ph)与[Ru_3(CO)_(12)]或[RuCl(η_3-烯丙基)(CO)_3]在甲苯中于高温下反应，得到三种PNP-钳形配合物1~3。后者具有一个不对称的PNP-钳形配体，在吡啶核心的2，6-位带有1-苯基-2-磷烯基和苯基(苯并[b]磷-1-基)甲基，这是通过在P═C键上加成t-Bu基团而形成的。另一方面，BPEP-Ph与[RuCl(η3-烯丙基)(CO)3]反应生成了含有脱芳基吡啶的不对称PNP钳形配体的二羰基Ru(II)氯(3)，在2，6-位上有1-苯基-2-磷烯基和α-(苯并[b]膦-1-基)亚甲基取代基。在四氢呋喃中，3与I-PROK反应可选择性地生成2.配合物1-3已被证实.
2,6-Bis[1-phenyl-2-(2,4,6-tri-tert-butylphenyl)-2-phosphaethenyl]pyridine (BPEP-Ph) reacts with [Ru3(CO)12] or [RuCl(η3-allyl)(CO)3] in toluene at elevated temperatures to afford the three types of PNP-pincer complexes 1–3. The reaction of BPEP-Ph with [Ru3(CO)12] under vacuum forms a mixture of [Ru(CO)2(BPEP-Ph)] (1) and a dicarbonylruthenium(0) complex (2); the latter complex has an unsymmetrical PNP-pincer ligand with 1-phenyl-2-phosphaethenyl and phenyl(benzo[b]phospholan-1-yl)methyl groups at the 2,6-positions of the pyridine core, which is formed by intramolecular C–H addition of a t-Bu group to the P═C bond. On the other hand, the reaction of BPEP-Ph with [RuCl(η3-allyl)(CO)3] affords a dicarbonylruthenium(II) chloride (3) with an unsymmetrical PNP-pincer ligand bearing a dearomatized pyridyl group with 1-phenyl-2-phosphaethenyl and α-(benzo[b]phospholan-1-yl)benzylidene substituents at the 2,6-positions. Treatment of 3 with i-PrOK in THF results in selective formation of 2. Complexes 1–3 have been...